EP3487934B1 - Compositions de polycarbonate resistantes aux rayures ayant une bonne stabilite thermique - Google Patents

Compositions de polycarbonate resistantes aux rayures ayant une bonne stabilite thermique Download PDF

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EP3487934B1
EP3487934B1 EP17743016.2A EP17743016A EP3487934B1 EP 3487934 B1 EP3487934 B1 EP 3487934B1 EP 17743016 A EP17743016 A EP 17743016A EP 3487934 B1 EP3487934 B1 EP 3487934B1
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weight
component
compositions according
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rubber
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EP3487934A1 (fr
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Kristina PUPOVAC
Hans-Jürgen KLANKERS
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Covestro Intellectual Property GmbH and Co KG
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/22—Emulsion polymerisation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
    • C08L69/005—Polyester-carbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/005—Additives being defined by their particle size in general
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/006—Additives being defined by their surface area
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/53—Core-shell polymer

Definitions

  • the present invention relates to impact-modified polycarbonate compositions, the use of the compositions for the production of moldings and the moldings themselves.
  • Moldings are produced from compositions containing polycarbonate and polymeric blend partners such as vinyl (co)polymers or polyesters for a large number of applications, for example in the automotive sector, in the construction sector, in the electrical/electronics sector and in household appliances. Due to the precise formulation, the compositions and thus also the moldings produced from them can be adapted to the requirements of the respective application in a wide range with regard to their thermal, rheological and mechanical properties.
  • polycarbonate and the moldings produced from polycarbonate compositions have a lower surface hardness than other thermoplastics, such as polymethyl methacrylate, and are therefore more sensitive to scratching. Scratches on the component surface are easily visible, especially on high-gloss molded parts, and are perceived as annoying. For this reason, moldings made from polycarbonate compositions are often provided with a scratch-resistant coating.
  • WO 2008/082225 A1 discloses compositions containing 100 parts by weight of a thermoplastic (A) and 0.1 to 50 parts by weight of metal oxide nanoparticles which have a surface modified with an organic silane and are improved in terms of scratch resistance.
  • WO 2013/079599 A1 discloses a thermoplastic molding composition made from polycarbonate and inorganic fillers which, in addition to increased rigidity, has high impact strength, elongation at break and good scratch resistance, which also persists when processed into molded parts with high-gloss surfaces.
  • CN 105176037A discloses a polycarbonate composition containing ABS, reinforcing additive, antioxidant and mold release agent.
  • the reinforcement additive contains Silica particles with a particle size of 2-4 ⁇ m.
  • the composition features good low-temperature toughness, strength and heat resistance.
  • WO 2008/061644 A discloses impact-modified compositions containing aromatic polycarbonate and/or aromatic polyester carbonate, rubber-modified graft polymer, hollow glass beads, phosphorus-containing flame retardant, vinyl (co)polymer and/or polyalkylene terephthalate and additives, which are characterized by improved flowability, high rigidity and low processing shrinkage with unchanged high scratch resistance award.
  • WO 2011/073291 A1 describes flame-retardant, impact-modified and scratch-resistant polycarbonate compositions with surface-modified, calcined kaolin as a filler, which have good mechanical properties, good flowability and high chemical resistance.
  • WO 2011/073290 A1 discloses scratch-resistant and impact-modified polycarbonate compositions with good mechanical properties and high chemical resistance.
  • the compositions contain a hard inorganic compound and a polyorganosiloxane keel compound.
  • polycarbonate compositions which are characterized by good gloss retention of high-gloss moldings after an abrasion test based on DIN EN 13300 and high stability of the melt volume flow rate when stored at high temperatures.
  • compositions according to the claims relate to 100% by weight of the compositions according to the claims.
  • the proportions of components A to D are selected in such a way that the sum of the % by weight of the individual components does not exceed 100 % by weight.
  • compositions consist of components A to D and the proportions of the components are selected such that the sum of the % by weight is 100.
  • the moldings have good resistance to sunscreen.
  • component A contains an aromatic polycarbonate based on bisphenol A with a weight-average molar mass M w of 24 kg/mol to 33 kg/mol, determined by gel permeation chromatography in methylene chloride using polycarbonate as the standard, and a polyester. If component A contains a polyester, then this is preferably used in a proportion of 15 to 50 % by weight, more preferably in a proportion of 20 to 45 % by weight, based on the composition according to the claims.
  • the invention also relates to scratch-resistant molded articles with a surface gloss of at least 95 at a viewing angle of 60° with an evaluation of the sunscreen resistance according to BMW test specification PR551 (as of 2014) with a sunscreen test mixture according to DBL 7384 of at least 6.
  • the scratch resistance is Based on DIN EN 13300 on the high-gloss panels with brush heads made of pig bristles (DIN 53778) using a dry process (dry abrasion) and a total of ten cycles (strokes). Scratch-resistant moldings are those moldings which lose less than 15% of their gloss under these test conditions.
  • Aromatic polycarbonates based on bisphenol A with a weight-average molar mass M w of 24 kg/mol to 33 kg/mol determined by gel permeation chromatography in methylene chloride with polycarbonate as standard, polyester carbonates and polyesters are used as component A.
  • aromatic polycarbonates based on bisphenol A with a weight-average molar mass M w of 24 kg/mol to 33 kg/mol, determined by gel permeation chromatography in methylene chloride with polycarbonate as the standard, are used as component A.
  • mixtures of these aromatic polycarbonates and polyesters are used. If such mixtures are used, the proportion of polyesters is 15 to 50 % by weight, preferably 20 to 45 % by weight, based on the claimed compositions of components A, B, C and D.
  • Aromatic polycarbonates and polyester carbonates suitable according to the invention according to component A are known from the literature or can be prepared by processes known from the literature (for the preparation of aromatic polycarbonates see, for example Schnell, “Chemistry and Physics of Polycarbonates", Interscience Publishers, 1964 as well as the DE-AS 1 495 626 , DE-A 2 232 877 , DE-A 2 703 376 , DE-A 2 714 544 , DE-A 3 000 610 , DE-A 3 832 396 ; for the production of aromatic polyester carbonates, e.g. B. DE-A 3 077 934 ).
  • aromatic polycarbonates and polyester carbonates takes place, for. B. by reacting 2,2-bis-(4-hydroxyphenyl)propane (bisphenol A) with carbonic acid halides, preferably phosgene, and/or with aromatic dicarboxylic acid dihalides, preferably benzenedicarboxylic acid dihalides, by the phase interface process, optionally using chain terminators, for example Monophenols and optionally using trifunctional or more than trifunctional branching agents, for example triphenols or tetraphenols. Production via a melt polymerization process by reacting bisphenol A with, for example, diphenyl carbonate is also possible.
  • Chain terminators suitable for the production of thermoplastic, aromatic polycarbonates are, for example, phenol, p-chlorophenol, p-tert-butylphenol or 2,4,6-tribromophenol, but also long-chain alkylphenols such as 4-[2-(2,4,4 -trimethylpentyl)]-phenol, 4-(1,3-tetramethylbutyl)-phenol according to DE-A 2 842 005 or monoalkylphenols or dialkylphenols having a total of 8 to 20 carbon atoms in the alkyl substituents, such as 3,5-di-tert-butylphenol, p-iso-octylphenol, p-tert-octylphenol, p-dodecylphenol and 2-(3,5- dimethylheptyl) phenol and 4-(3,5-dimethylheptyl) phenol.
  • the amount of chain terminators to be used is generally between 0.5 mol % and 10 mol %,
  • Aromatic dicarboxylic acid dihalides for the production of aromatic polyester carbonates are preferably the diacid dichlorides of isophthalic acid, terephthalic acid, diphenyl ether-4,4'-dicarboxylic acid and naphthalene-2,6-dicarboxylic acid.
  • Mixtures of the diacid dichlorides of isophthalic acid and terephthalic acid in a ratio of between 1:20 and 20:1 are particularly preferred.
  • a carbonic acid halide preferably phosgene, is also used as a bifunctional acid derivative.
  • chain terminators used in the preparation of the aromatic polyester carbonates are their chlorocarbonic acid esters and the acid chlorides of aromatic monocarboxylic acids, which may be substituted by C.sub.1 to C.sub.22 -alkyl groups or by halogen atoms, and aliphatic C.sub.2 to C.sub.22 -monocarboxylic acid chlorides under consideration.
  • the amount of chain terminators is in each case 0.1 to 10 mol %, based on moles of diphenol in the case of phenolic chain terminators and on moles of dicarboxylic acid dichloride in the case of monocarboxylic acid chloride chain terminators.
  • the aromatic polyester carbonates can also contain built-in aromatic hydroxycarboxylic acids.
  • the aromatic polyester carbonates can be either linear or branched in a known manner (see DE-A 2 940 024 and DE-A 3 007 934 ).
  • branching agents which can be used are trifunctional or polyfunctional carboxylic acid chlorides, such as trimesic acid trichloride, cyanuric acid trichloride, 3,3'-,4,4'-benzophenonetetracarboxylic acid tetrachloride, 1,4,5,8-naphthalenetetracarboxylic acid tetrachloride or pyromellitic acid tetrachloride, in amounts of 0.01 up to 1.0 mol% (based on the dicarboxylic acid dichlorides used) or trifunctional or polyfunctional phenols such as phloroglucinol, 4,6-dimethyl-2,4,6-tri-(4-hydroxyphenyl)-hept-2-ene, 4, 6-dimethyl-2,4-6-tri-(4-hydroxyphenyl)-heptane, 1,3,5-tri-(4-hydroxyphenyl)-benzene, 1,1,1-tri-(4-hydroxyphenyl)- ethane,
  • the proportion of carbonate structural units in the thermoplastic, aromatic polyester carbonates can vary as desired.
  • the proportion of carbonate groups is preferably up to 100 mol % , in particular up to 80 mol % , particularly preferably up to 50 mol % , based on the sum of ester groups and carbonate groups.
  • Both the ester and the carbonate portion of the aromatic polyester carbonates can be in the form of blocks or randomly distributed in the polycondensate.
  • the relative solution viscosity ( ⁇ rel ) of the aromatic polycarbonates and polyester carbonates is preferably in the range from 1.18 to 1.4, particularly preferably in the range from 1.20 to 1.32 (measured according to DIN 51652 in the 1999 version on solutions of 0, 5 g polycarbonate or polyester carbonate in 100 ml methylene chloride at 25°C).
  • the weight-average molecular weight Mw of the aromatic polyester carbonates is preferably in the range from 15 to 36 kg/mol, more preferably in the range from 20 to 34 kg/mol, particularly preferably 24 to 33 kg/mol, determined by GPC (gel permeation chromatography in methylene chloride with polycarbonate as the standard).
  • the weight-average molecular weight Mw of the aromatic polycarbonates based on bisphenol A is in the range from 24 to 33 kg/mol, determined by GPC (gel permeation chromatography in methylene chloride with polycarbonate as the standard).
  • polyesters which are suitable as a constituent of component A are aromatic, more preferably they are polyalkylene terephthalates.
  • these are reaction products from aromatic dicarboxylic acids or their reactive derivatives, such as dimethyl esters or anhydrides, and aliphatic, cycloaliphatic or araliphatic diols and mixtures of these reaction products.
  • Particularly preferred polyalkylene terephthalates contain at least 80 % by weight, preferably at least 90 % by weight, based on the dicarboxylic acid component, of terephthalic acid residues and at least 80 % by weight, preferably at least 90 % by weight, based on the diol component, of ethylene glycol and/or butanediol 1,4 residues.
  • the preferred polyalkylene terephthalates can contain up to 20 mol % , preferably up to 10 mol %, residues of other aromatic or cycloaliphatic dicarboxylic acids having 8 to 14 carbon atoms or aliphatic dicarboxylic acids having 4 to 12 carbon atoms, such as residues of phthalic acid , isophthalic acid, naphthalene-2,6-dicarboxylic acid, 4,4'-diphenyldicarboxylic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, cyclohexanediacetic acid.
  • the preferred polyalkylene terephthalates can contain up to 20 mol %, preferably up to 10 mol %, of other aliphatic diols having 3 to 12 carbon atoms or cycloaliphatic diols having 6 to 21 carbon atoms, for example residues of 1,3-propanediol, 2-ethyl1,3-propanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexane dimethanol, 3-2,4-ethylpentanediol, 2-methylpentanediol -2,4, 2,2,4-Trimethylpentanediol-1,3, 2-ethylhexanediol-1,3, 2,2-diethylpropanediol-1,3, hexanedi
  • the polyalkylene terephthalates can by incorporating relatively small amounts of 3- or 4-hydric alcohols or 3- or 4-basic carboxylic acids, for example according to DE-A 1 900 270 and U.S. Patent 3,692,744 , to be branched.
  • preferred branching agents are trimesic acid, trimellitic acid, trimethylolethane and trimethylolpropane and pentaerythritol.
  • polyalkylene terephthalates which have been prepared solely from terephthalic acid and its reactive derivatives (e.g. its dialkyl esters) and ethylene glycol and/or butane-1,4-diol, and mixtures of these polyalkylene terephthalates.
  • Polyalkylene terephthalates contain 1 to 50% by weight, preferably 1 to 30% by weight, polyethylene terephthalate and 50 to 99% by weight, preferably 70 to 99% by weight, polybutylene terephthalate.
  • the polyalkylene terephthalates preferably used preferably have an intrinsic viscosity of 0.4 to 1.5 dl/g, preferably 0.5 to 1.2 dl/g, measured in the Ubbelohde viscometer Dichloroacetic acid in a concentration of 1% by weight at 25°C according to DIN 53728-3.
  • the determined intrinsic viscosity is calculated from the measured specific viscosity x 0.0006907 + 0.063096.
  • Polybutylene terephthalate is particularly preferably used as the polyester.
  • the particularly preferred polybutylene terephthalates have a melt flow rate of 9 g/10 min to 60 g/10 min, measured according to DIN EN ISO 1133 at 250° C. and a load of 2.16 kg.
  • the polyalkylene terephthalates can be prepared by known methods (see, for example, Kunststoff-Handbuch, Volume VIII, p. 695 ff., Carl-Hanser-Verlag, Kunststoff 1973 ).
  • Component B is a rubber-modified graft polymer.
  • Component B can also contain rubber-free vinyl (co)polymer.
  • Component B comprises graft polymers produced by the emulsion polymerization process (component B1) and optionally additional rubber-modified graft polymers produced by the bulk, solution or suspension polymerization process (component B2). Due to the manufacturing process, components B1 and B2 contain free vinyl (co)polymer, i.e. vinyl (co)polymer not bonded to the rubber base. Rubber-free vinyl (co)polymer can also be added as a separate component (component B3).
  • component B consists only of B1.
  • compositions according to the invention contain 5 to 15% by weight of B1, based on the compositions of components A, B, C and D according to the claims.
  • the graft base preferably has a glass transition temperature ⁇ 0°C, more preferably ⁇ -20°C, particularly preferably ⁇ -60°C.
  • glass transition temperatures are determined by means of differential scanning calorimetry (DSC) according to the standard DIN EN 61006 at a heating rate of 10 K/min with the definition of Tg as the midpoint temperature (tangent method) and nitrogen as the protective gas.
  • DSC differential scanning calorimetry
  • mixture B.1.1 is also referred to as the graft of component B.1.
  • the graft particles in component B1 preferably have an average particle size (d 50 value) of from 0.05 to 5 ⁇ m, preferably from 0.1 to 1.0 ⁇ m, particularly preferably from 0.2 to 0.5 ⁇ m.
  • the average particle size d 50 is the diameter above and below which 50% by weight of the particles are in each case. In the context of the present patent application, it is measured using ultracentrifuges ( W. Scholtan, H. Lange, Colloid, Z. and Z. Polymere 250 (1972), 782-1796 ) certainly.
  • Preferred monomers B1.1.1 are selected from at least one of the monomers styrene, ⁇ -methylstyrene and methyl methacrylate
  • preferred monomers B1.1.2 are selected from at least one of the monomers acrylonitrile, maleic anhydride and methyl methacrylate.
  • graft bases B1.2 suitable for the graft polymers B1 are diene rubbers, diene-vinyl block copolymer rubbers, EP(D)M rubbers, ie those based on ethylene/propylene and optionally diene, acrylate, polyurethane, silicone and chloroprene - and ethylene/vinyl acetate rubbers and mixtures of such rubbers or silicone-acrylate composite rubbers in which the silicone and acrylate components are chemically linked to one another (e.g. by grafting).
  • Preferred graft bases B1.2 are diene rubbers (e.g. based on butadiene or isoprene), diene-vinyl block copolymer rubbers (e.g. based on butadiene and styrene blocks), copolymers of diene rubbers with other copolymerizable monomers (e.g. according to B1.1.1 and B1 .1.2) and mixtures of the aforementioned types of rubber. Pure polybutadiene rubber and styrene-butadiene block copolymer rubber are particularly preferred.
  • Graft polymer according to component B1 are preferably ABS polymers produced in the emulsion polymerization process, as for example in Ullmanns, Encyclopedia of Technical Chemistry, Vol. 19 (1980), p. 280 ff . are described.
  • the graft polymer composed of components B1.1 and B1.2 preferably has a core-shell structure, with component B.1 forming the shell (also referred to as the shell) and component B.2 forming the core (see, for example, Ullmann's Encyclopedia of Industrial Chemistry, VCH-Verlag, Vol. A21, 1992, page 635 and page 656 .
  • ABS polymers which, in the emulsion polymerization process, are produced by redox initiation using an initiator system composed of organic hydroperoxide and ascorbic acid U.S. Patent 4,937,285 getting produced.
  • graft polymers B1 are MBS modifiers with a core-shell structure.
  • the gel content of the graft polymers is at least 40% by weight, preferably at least 60% by weight, particularly preferably at least 75% by weight (measured in acetone).
  • the gel content of the graft polymers is determined at 25° C. as the fraction insoluble in acetone as solvent ( M. Hoffmann, H. Krömer, R. Kuhn, Polymer analysis I and II, Georg Thieme-Verlag, Stuttgart 1977 ).
  • the graft polymers B1 are prepared by free-radical polymerization.
  • the graft polymer B1 generally comprises free copolymer from B1.1.1 and B1.1.2, i.e. not chemically bonded to the rubber base, which is characterized in that it can be dissolved in suitable solvents (e.g. acetone).
  • suitable solvents e.g. acetone
  • Component B1 preferably contains a free copolymer of B1.1.1 and B1.1.2 which has a weight-average molecular weight (Mw), determined by gel permeation chromatography in tetrahydrofuran using polystyrene as the standard, of 20 to 180 kg/mol, preferably 30 to 150 kg/mol. mol, particularly preferably from 40 to 140 kg/mol.
  • Mw weight-average molecular weight
  • the graft base preferably has a glass transition temperature ⁇ 0°C, preferably ⁇ -20°C, particularly preferably ⁇ -60°C.
  • mixture B.2.1 is also referred to as the graft of component B.2.
  • the graft particles in component B2 preferably have an average particle size (D50 value) of 0.1 to 10 ⁇ m, preferably 0.2 to 2 ⁇ m, particularly preferably 0.3 to 1.0 ⁇ m, very particularly preferably 0 .3 to 0.9 ⁇ m.
  • Preferred monomers B2.1.1 are selected from at least one of the monomers styrene, ⁇ -methylstyrene and methyl methacrylate
  • preferred monomers B2.1.2 are selected from at least one of the monomers acrylonitrile, maleic anhydride and methyl methacrylate.
  • Particularly preferred monomers are B2.1.1 styrene and B2.1.2 acrylonitrile.
  • graft bases B2.2 suitable for the graft polymers B2 are diene rubbers, diene-vinyl block copolymer rubbers, EP(D)M rubbers, ie those based on ethylene/propylene and optionally diene, acrylate, polyurethane, silicone and chloroprene - and ethylene/vinyl acetate rubbers and mixtures of such rubbers or silicone-acrylate composite rubbers in which the silicone and acrylate components are chemically linked to one another (e.g. by grafting).
  • diene rubbers diene-vinyl block copolymer rubbers
  • EP(D)M rubbers ie those based on ethylene/propylene and optionally diene
  • acrylate polyurethane
  • silicone and chloroprene - and ethylene/vinyl acetate rubbers and mixtures of such rubbers or silicone-acrylate composite rubbers in which the silicone and acrylate components are chemically linked to one another (e.g.
  • Preferred graft bases B2.2 are diene rubbers (e.g. based on butadiene or isoprene), diene-vinyl block copolymer rubbers (e.g. based on butadiene and styrene blocks), copolymers of diene rubbers with other copolymerizable monomers (e.g. according to B2.1.1 and B2 .1.2) and mixtures of the aforementioned types of rubber.
  • Styrene-butadiene block copolymer rubbers and mixtures of styrene-butadiene block copolymer rubbers with pure polybutadiene rubber are particularly preferred as the graft base B2.2.
  • the gel content of the graft polymers B2 is preferably 10 to 35% by weight, particularly preferably 15 to 30% by weight, very particularly preferably 17 to 23% by weight (measured in acetone).
  • Particularly preferred polymers B2 are, for example, ABS polymers produced by free-radical polymerization, which in a preferred embodiment contain up to 10% by weight, particularly preferably up to 5% by weight, particularly preferably 2 to 5% by weight, based in each case on the Graft polymer B2 containing n-butyl acrylate.
  • the graft polymer B2 generally comprises copolymer of B2.1.1 and B2.1.2 that is free due to the production process, i.e. not chemically bonded to the rubber base, which is characterized in that it can be dissolved in suitable solvents (e.g. acetone).
  • suitable solvents e.g. acetone
  • Component B2 preferably contains free copolymer of B2.1.1 and B2.1.2, which has a weight-average molecular weight (Mw), determined by gel permeation chromatography in tetrahydrofuran with polystyrene as standard, preferably from 50 to 200 kg/mol, particularly preferably from 70 to 150 kg/mol, particularly preferably from 80 to 140 kg/mol.
  • Mw weight-average molecular weight
  • the composition can optionally contain (co)polymers of at least one monomer from the group consisting of vinyl aromatics, vinyl cyanides (unsaturated nitriles), (meth)acrylic acid-(C1 to C8)-alkyl esters, unsaturated carboxylic acids and derivatives (such as anhydrides and imides ) of unsaturated carboxylic acids.
  • These (co)polymers B3 are resinous, thermoplastic and free from rubber.
  • the copolymer of B3.1 styrene and B3.2 acrylonitrile is particularly preferred.
  • Such (co)polymers B3 are known and can be prepared by free-radical polymerization, in particular by emulsion, suspension, solution or bulk polymerization.
  • the (co)polymers B3 have a weight-average molecular weight (Mw), determined by gel permeation chromatography in tetrahydrofuran using polystyrene as the standard, of preferably 50 to 200 kg/mol, particularly preferably 70 to 150 kg/mol, particularly preferably 80 to 140 kg /mol
  • Mw weight-average molecular weight
  • the thermoplastic molding compositions contain an inorganic filler which is more than 98% by weight based on silicon dioxide (quartz).
  • silicon dioxide quartz
  • the thermoplastic molding compositions contain an inorganic filler which is more than 98% by weight based on silicon dioxide (quartz).
  • quartz powders are produced from electrically melted silicon dioxide by iron-free grinding with subsequent air classification.
  • Particularly preferred quartz material is characterized in that the content of metal oxides does not exceed 2% by weight, preferably 1.5% by weight, particularly preferably 1% by weight, the content of Al 2 O 3 preferably being ⁇ 1% by weight. %, preferably ⁇ 0.6% by weight, particularly preferably ⁇ 0.3% by weight, FejOs ⁇ 0.1% by weight, preferably ⁇ 0.06% by weight, particularly preferably ⁇ 0.03% by weight.
  • the quartz material is characterized in that the Al 2 O 3 content is 0.01 to 1% by weight, preferably 0.05 to 0.6% by weight, particularly preferably 0.1 to 0.3% by weight .-% amounts to.
  • the quartz material is characterized in that the Fe 2 O 3 content is 0.001 to 0.1% by weight, preferably 0.005 to 0.06% by weight, particularly preferably 0.01 to 0.03% by weight. -% amounts to.
  • the quartz material is characterized in that the CaO+MgO content is 0.001 to 0.1% by weight, preferably 0.005 to 0.06% by weight, particularly preferably 0.01 to 0.03% by weight. % amounts to.
  • the quartz material is characterized in that the Na 2 O+K 2 O content is 0.001 to 0.1% by weight, preferably 0.005 to 0.06% by weight, particularly preferably 0.01 to 0. 03% by weight.
  • quartz powder according to the invention with an average particle size d 50 of 1.0 to 10.0 ⁇ m, preferably 2.0 to 6.0 ⁇ m and particularly preferably of 3.0 to 5.0 ⁇ m is particularly advantageous and preferred.
  • the average particle size d 50 is the diameter above and below which 50% by weight of the particles are in each case. It can be measured using an ultracentrifuge ( W. Scholtan, H. Lange, Colloid, Z. and Z. Polymere 250 (1972), 782-1796 ) are determined.
  • the quartz material to be used according to the invention preferably has an upper particle or grain size d 90 of less than 100 ⁇ m, preferably less than 50 ⁇ m, particularly preferably less than 20 ⁇ m and particularly preferably less than 15 ⁇ m.
  • the upper particle or Grain size d 90 denotes the size that 90% of the particles or grains do not exceed.
  • the fused silica powder preferably has a specific BET surface area, determined by nitrogen adsorption in accordance with ISO 9277 (2010 version), from 0.6 to 10.0 m 2 /g, more preferably from 2.0 to 8.0 m 2 /g and more preferably from 5.0 to 7.0 m 2 /g.
  • quartz powders which have a pH value, measured according to ISO 10390 (2005 version) in aqueous suspension, in the range from 5.0 to 8.0, preferably from 5.5 to 7.0.
  • they have an oil absorption number according to ISO 787-5 (1995 version) of preferably 20 to 30 g/100 g.
  • compositions can contain at least one additive different from component C as component D, preferably selected from the group consisting of flame retardants (e.g. organic phosphorus or halogen compounds, in particular bisphenol A-based oligophosphate), anti-dripping agents (e.g. compounds of the substance classes of fluorinated polyolefins, silicones and aramid fibers), flame retardant synergists (e.g. nanoscale metal oxides), smoke inhibitors (e.g. zinc borate), lubricants and mold release agents (e.g. pentaerythritol tetrastearate), nucleating agents, antistatic agents, conductivity additives, stabilizers (e.g.
  • flame retardants e.g. organic phosphorus or halogen compounds, in particular bisphenol A-based oligophosphate
  • anti-dripping agents e.g. compounds of the substance classes of fluorinated polyolefins, silicones and aramid fibers
  • flame retardant synergists
  • fillers and reinforcing materials e.g. carbon fibers, talc, mica, kaolin, CaCOs
  • dyes and pigments e.g. titanium dioxide or iron oxide
  • compositions are free from flame retardants, anti-drip agents, flame retardant synergists and smoke inhibitors.
  • compositions contain at least one polymer additive selected from the group consisting of lubricants and mold release agents, stabilizers, flow promoters, compatibilizers, other impact modifiers other than component B, other polymeric components, dyes and pigments.
  • compositions contain at least one polymer additive selected from the group consisting of lubricants/mould release agents and stabilizers.
  • compositions contain pentaerythritol tetrastearate as a mold release agent.
  • compositions contain at least one representative selected from the group consisting of sterically hindered phenols, organic stabilizers Phosphites, sulphur-based co-stabilizers and organic and inorganic Brönsted acids.
  • compositions contain as a stabilizer at least one representative selected from the group consisting of octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, tris(2,4-di-tert-butylphenyl) phosphite and phosphorous acid.
  • Molding compositions can be produced from the compositions according to the invention containing components A to D.
  • the components are mixed in a known manner and melt-compounded or melt-extruded at temperatures of from 200° C. to 330° C. in customary units such as internal kneaders, extruders and twin-shaft screws.
  • compositions (molding masses) produced by the process according to the invention can be used to produce any type of molding. These can be produced, for example, by injection moulding, extrusion and blow molding processes. Another form of processing is the production of shaped bodies by deep-drawing from previously produced sheets or foils.
  • moldings are foils, profiles, housing parts of all kinds, for example for household appliances such as juicers, coffee machines, mixers; for office machines such as monitors, flat screens, notebooks, printers, copiers; Plates, pipes, electrical installation ducts, windows, doors and other profiles for the construction sector (interior and exterior applications) as well as electrical and electronic parts such as switches, plugs and sockets and components for commercial vehicles, especially for the automotive sector.
  • household appliances such as juicers, coffee machines, mixers
  • office machines such as monitors, flat screens, notebooks, printers, copiers
  • Plates pipes, electrical installation ducts, windows, doors and other profiles for the construction sector (interior and exterior applications) as well as electrical and electronic parts such as switches, plugs and sockets and components for commercial vehicles, especially for the automotive sector.
  • compositions according to the invention are also suitable for the production of the following moldings or moldings: interior fittings for rail vehicles, ships, aircraft, buses and other motor vehicles, body parts for motor vehicles, housings for electrical devices containing small transformers, housings for devices for information processing and transmission, housings and linings Medical devices, massage devices and housings therefor, toy vehicles for children, flat wall elements, housings for safety devices, heat-insulated transport containers, molded parts for sanitary and bathing equipment, cover grilles for fan openings and housings for garden tools.
  • compositions according to the invention are particularly suitable for producing high-gloss interior and exterior parts for automobiles and rail vehicles.
  • Another form of processing is the production of moldings by blow molding or by deep drawing from previously produced sheets or foils.
  • compositions according to the invention for the production of moldings and moldings or moldings of any kind obtainable from the compositions according to the invention.
  • Component A-1 is a compound having Component A-1:
  • Linear polycarbonate based on bisphenol-A with a weight average molecular weight Mw of 25kg/mol determined by GPC in methylene chloride using polycarbonate standards.
  • Component A-2 is a compound having Component A-2:
  • Linear polycarbonate based on bisphenol-A with a weight average molecular weight Mw of 32kg/mol (determined by GPC in methylene chloride using polycarbonate standards).
  • Polybutylene terephthalate (Pocan TM B1600, Lanxess AG) with a melt volume flow rate (MVR) of 14 cm 3 /10 min measured at 260°C/2.16kg (ISO 1133).
  • Polybutylene terephthalate (Pocan TM B1300, Lanxess AG) with a melt volume flow rate (MVR) of 45 cm 3 /10 min measured at 250°C/2.16kg (ISO 1133).
  • ABS Acrylonitrile butadiene styrene
  • Impact modifier with a core/shell structure Core: polybutadiene, shell: polymethyl methacrylate (Paraloid TM EXL 2690, Dow).
  • ABS Acrylonitrile Butadiene Styrene
  • A:B:S ratio 19:25:56.
  • the mean rubber particle size d 50 measured by ultracentrifugation, is 0.25 ⁇ m.
  • Component B3 contains free copolymer of styrene and acrylonitrile, which has a weight-average molecular weight (Mw), determined by gel permeation chromatography using polystyrene as the standard, of 130 kg/mol.
  • ABS Acrylonitrile Butadiene Styrene
  • Styrene-acrylonitrile copolymer with an acrylonitrile content of 23% by weight and a weight-average molecular weight of about 130 kg/mol (determined by GPC in tetrahydrofuran using polystyrene as the standard).
  • the fused silica has a pH of 6 measured according to ISO 10390.
  • the quartz powder has a specific BET surface area, determined by nitrogen adsorption according to ISO 9277 (2010 version), of 6.0 m 2 /g.
  • Component C-3 Vinylsilane-modified calcined kaolin (aluminum silicate), Burgess CB TM from Burgess Pigment Company (USA) with an average particle size of 1.5 ⁇ m.
  • Component D-1 Irganox TM 1076 (2,6-di-tert-butyl-4-(octadecanoxycarbonylethyl)-phenol), BASF (Ludwigshafen, Germany).
  • Component D-2 phosphorous acid ester of bis-(2-hydroxy-3-cyclohexyl-5-methyl-phenyl)-methane, commercially available from Rhein Chemie Rheinau GmbH under the name Addovate ThermoStab.
  • Component D-3 phosphorous acid (Sigma-Aldrich Chemie GmbH).
  • Component D-4 UV stabilizer Tinuvin TM 360 (BASF). 2,2'-Methylenebis[6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol].
  • Component D-5 pentaerythritol tetrastearate, Loxiol TM P 861/3.5 Special (Emery Oleochemicals GmbH).
  • Component D-7 Carbon black, Black pearls TM (Cabot Corporation).
  • the components were mixed on a Werner & Pfleiderer ZSK-25 twin-screw extruder at a melt temperature of 260.degree.
  • the molded bodies were produced at a melt temperature of 260° C. and a mold temperature of 150° C. (Table 1, Examples 1-7) or 110° C. (Table 2, Examples 8-14) using variothermal injection molding technology (Rapid Heat Cycle Molding (RHCM )) produced on an Arburg 270 E injection molding machine.
  • RHCM Remote Heat Cycle Molding
  • the measure of the thermal stability of the composition is the change in MVR (in %) measured according to ISO 1133 (2012 version) at 260°C with a stamp load of 5 kg during a 15-minute thermal load at 300°C (Table 1 , Examples 1-7) or during a 15-minute thermal load at 260°C (Table 2, Examples 8-10, 12-13).
  • the abrasion resistance test was carried out using an abrasion tester from BYK-Gardner (PB-5000) based on DIN EN 13300 (2001 version).
  • the abrasion resistance was tested on the high-gloss panels (160 ⁇ 110 ⁇ 3 mm, obtained by means of RHCM) with brush heads made from pig bristles (DIN 53778) using a dry method (dry abrasion) and a total of ten cycles (strokes). Based on means that, deviating from the standard, a dry method (dry abrasion) was used and ten cycles (strokes) were carried out.
  • the degree of gloss was then measured.
  • the measure of the scratch resistance is the change in the gloss level (in %), measured using a gloss level measuring device (reflectometer) at a measuring angle of 60° from BYK-Gardner.
  • the sunscreen resistance was tested according to the BMW test specification PR551 (as of 2014) with a sunscreen test mixture according to DBL 7384.
  • the test specimen (high-gloss panel) was loaded with the test cream by dropping it, the size of the drop having a diameter of ⁇ 7-10 mm.
  • the specimen was then stored in a heating oven at 60 ⁇ 2°C for 24 hours.
  • the specimens were stored horizontally and the drops were at least 12mm from the specimen edges.
  • the evaluation was carried out visually according to the criteria of the test specification. A rating of 4 indicates a clear optical defect after the test, while a rating of 7 corresponds to a slight change after the test. Completely unchanged surfaces are rated with the indexes 9 and 10.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Claims (14)

  1. Compositions contenant
    A) 50 à 90 % en poids d'au moins un polymère choisi dans le groupe constitué par un polycarbonate aromatique à base de bisphénol A doté d'une masse molaire moyenne en poids Mw de 24 kg/mole à 33 kg/mole déterminée par chromatographie à perméation de gel dans du chlorure de méthylène avec un polycarbonate en tant que référence, un polyestercarbonate aromatique et un polyester,
    B) 5 à 40 % en poids d'au moins un polymère greffé modifié par un caoutchouc,
    C) 1 à 20 % en poids de silice vitreuse dotée d'une taille moyenne de particule dso, qui est mesurée comme expliqué dans la partie expérimentale de la description, de 1,0 à 10,0 µm et d'une teneur en oxydes métalliques ≤ 2 % en poids par rapport au composant C,
    D) 0 à 20 % en poids d'au moins un additif différent du composant C.
  2. Compositions selon la revendication 1, le composant B contenant un polymère greffé préparé dans un procédé de polymérisation en émulsion avec un caoutchouc de butadiène en tant que base de greffage et un revêtement de greffage composé de méthacrylate de méthyle ou d'un copolymère de styrène-acrylonitrile.
  3. Compositions selon l'une quelconque des revendications précédentes, le composant C présentant une teneur en oxyde d'aluminium de ≤ 1 % en poids.
  4. Compositions selon l'une quelconque des revendications précédentes, le composant C présentant une teneur en Fe2O3 de ≤ 0,1 % en poids.
  5. Compositions selon l'une quelconque des revendications précédentes, le composant C présentant une taille moyenne de particule dso, qui est mesurée comme expliqué dans la partie expérimentale de la description, de 3 à 5 pm.
  6. Compositions selon l'une quelconque des revendications précédentes, le composant C présentant une valeur de pH, déterminée selon la norme DIN ISO 10390, de 5 à 6,5.
  7. Compositions selon l'une quelconque des revendications précédentes, le composant C présentant une surface spécifique BET, déterminée par adsorption d'azote selon la norme ISO 9277, de 2,0 m2/g à 8,0 m2/g.
  8. Compositions selon l'une quelconque des revendications précédentes, le composant A comprenant seulement un polycarbonate aromatique à base de bisphénol A doté d'une masse molaire moyenne en poids Mw de 24 kg/mole à 33 kg/mole déterminée par chromatographie à perméation de gel dans du chlorure de méthylène avec un polycarbonate en tant que référence et le composant B comprenant un polymère greffé modifié par un caoutchouc préparé par polymérisation en émulsion et au moins un polymère, choisi parmi un polymère greffé modifié par un caoutchouc, préparé par un procédé de polymérisation en masse, en solution ou en suspension et un (co)polymère vinylique exempt de caoutchouc.
  9. Compositions selon l'une quelconque des revendications 1 à 7, le composant A contenant un polycarbonate aromatique à base de bisphénol A doté d'une masse molaire moyenne en poids Mw de 24 kg/mole à 33 kg/mole déterminée par chromatographie à perméation de gel dans du chlorure de méthylène avec un polycarbonate en tant que référence et un poly(téréphtalate d'alkylène) ou un mélange de plusieurs poly(téréphtalate d'alkylène) et le composant B étant seulement constitué d'un polymère greffé modifié par un caoutchouc préparé par polymérisation en émulsion.
  10. Compositions selon la revendication 9, un poly(téréphtalate de butylène) étant utilisé en tant que poly(téréphtalate d'alkylène).
  11. Compositions selon l'une quelconque des revendications 1 à 7 et 9 à 10, le polyester étant contenu en une proportion de 20 à 45 % en poids par rapport aux compositions selon les revendications.
  12. Compositions selon l'une quelconque des revendications précédentes contenant 5 à 15 % en poids d'un polymère greffé modifié par un caoutchouc préparé par polymérisation en émulsion.
  13. Utilisation de compositions selon l'une quelconque des revendications 1 à 12 pour la préparation de corps moulés.
  14. Corps moulé pouvant être obtenu à partir de compositions selon l'une quelconque des revendications 1 à 12.
EP17743016.2A 2016-07-22 2017-07-21 Compositions de polycarbonate resistantes aux rayures ayant une bonne stabilite thermique Active EP3487934B1 (fr)

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EP3794073B1 (fr) * 2018-05-17 2023-07-26 Covestro Intellectual Property GmbH & Co. KG Compositions de polycarbonate chargées présentant une bonne résistance aux rayures et un jaunissement réduit
WO2022239938A1 (fr) 2021-05-10 2022-11-17 (주) 엘지화학 Composition de résine composite pour matériau intérieur d'automobile et matériau intérieur d'automobile l'utilisant

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US10899925B2 (en) 2021-01-26
TW201817810A (zh) 2018-05-16
TWI752058B (zh) 2022-01-11
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CN109476906A (zh) 2019-03-15
CN109476906B (zh) 2021-08-27

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